Studies in nuclear magnetic resonance—IX. Rotational barriers in substituted N,N-dimethylbenzamides

The barriers to rotation about the C? N bond in eighteen substituted N,N-dimethylbenzamides have been determined by complete line shape analysis of the NMR spectra of the N,N-dimethyl protons. The barriers have been correlated with the substituent constants σ and σ⁺. It has been shown that polar solvents increase the barrier in N,N-dimethylbenzamide. Acid catalysis of rotation about the amide C? N bond in N-(p-N,N-dimethylcarboxamidobenzyl)-pyridinium bromide has been investigated. ¹⁸O exchange studies show that catalysis is due to N-protonation rather than the formation of a tetrahedral intermediate. The rate of rotation is a function of the Hammett acidity function, H₀, and the water activity, and it is shown that proton exchange between the N- and O-protonated species involves the intermediacy of a water molecule. The differences in chemical shifts for the non-equivalent N, N-dimethyl groups of the benzamides are also a function of the substituents. Possible explanations of this phenomenon are discussed.     

Conformational studies by nuclear magnetic resonance—V: 13C spectra and structural problems of enamino carbonyl compounds

A ¹³C magnetic resonance investigation of 22 compounds of the general formula O?C¹(R¹)C²(R²)?C³(R³) NR⁴R^4′ has been carried out in order to confirm the conformational assignments estimated previously by PMR and IR spectroscopy. The effects of nonplanarity and hindered rotation have been discussed based on chemical shifts and shapes of the C¹, C² and C³ signals.     

Conformational studies by nuclear magnetic resonance—IV: Restricted rotation in vinylogous thioamides

Enamino -thial and -thiones R¹C(S)CH?CHNR (R¹ = H or alkyl; R² = Me or Et) have been shown by NMR spectra to exist in two rotational forms, s-cis and s-trans, the populations of the latter being approximately the same as in the case of the parent oxa analogues. An increase of the order of 2 to 4 Kcal/mole in the heights of C? C and C? N rotation barriers (ΔG*) was found on comparing the title compounds with their oxa analogues. IR spectra failed as a tool to establish the rotational equilibrium. IR absorption bands of the ν_{C? C}, ν_{C? H} (in the NMe₂ group) and γ_HC?CH vibrations have been found, but the ν_C?S band could not be assigned unambiguously. Anomalies concerning the frequency and intensity of the ν_C?C band are discussed.     

Studies in organometallic rearrangements IV—proton and carbon nuclear magnetic resonance spectra of group IVA substituted indenes and indenyl anions

The proton and carbon NMR spectra for a series of substituted indenes [C₉H₇R, R = H, CH₃, Si(CH₃)₃] are reported. The proton and carbon resonances for the 5-membered ring exhibit pronounced changes as a function of the substituents.     

Carbon-13 nuclear magnetic resonance spectra: III—2-heteroadamantanes

The ¹³C n.m.r. spectra of some 2-heteroadamantanes and 1-substituted 2-heteroadamantanes are reported. The influences of the heteroatoms in the adamantane framework, and those of the substituents attached to it, on the ¹³C chemical shifts of the adamantane carbons are investigated and compared with related compounds such as the corresponding heterocyclohexane derivatives and 2-mono- and 2,2-disubstituted adamantanes. The nonadditivity of the substituent effects for 1-substituted 2-heteroadamantanes, especially for the geminally substituted carbons, is substantially confirmed. In addition, the influences of a missing CH₂ group and of NCH₃ carbons upon the ¹³C chemical shifts of the carbons in the adamantane system are described.     

Conformational studies by nuclear magnetic resonance—III: ASIS and protonation studies of the rotational isomerism of enamino aldehydes and ketones

The s-cis ? s-trans equilibrium of several enamino ketones and aldehydes, has been evaluated based on the results of aromatic solvent induced shift measurements and of protonation of the title compounds. In contrast to α,β-unsaturated ketones bearing no heteroatom, the Δδ_3,cis value but not the Δδ_3,trans, proved to be useful in conformational assignments. Protonation, which occurs mainly on oxygen, enhances the rotational barrier, thus enabling the observation of both rotamers at room temperature. Steric hindrance to conjugation enhances the rate of protonation at the carbon C².     

Terpenoids—II The nuclear magnetic resonance spectra of tetracyclic triterpenes

The methyl region in the NMR spectra of euphane and isoeuphane derivatives have been studied. Several signals were compared with data of other triterpenes of the dammarane and lupane series.     

Carbon-13 nuclear magnetic resonance spectra. I—Monosubstituted adamantanes and adamantanones

The chemical shifts of 4_ax and 4_eq substituted adamantanones are compared with those calculated with the aid of a given additivity rule. It is found that both δ carbons are shielded with respect to the substituent. In contract to the situation for the y-atoms, however, the δ_syn atom is less shielded than the δ_anti atom. In most cases the additivity rule predicts the chemical shifts with an accuracy of approximately 1 ppm. Exceptions are carbon atoms 4 and 9 of the 4_eq substituted adamantanones. In both cases the measured values are 4 to 6 ppm upfield. This can possibly be explained by an electronic interaction between the carbonyl group and the substituent.     

Carbon-13 nuclear magnetic resonance spectra: V—substituent interactions at 4-substituted adamantanones and bicyclo[2.2.2]octanones

The ¹³C n.m.r. data of a variety of 4_eq- and 4_ax-substituted adamantanones and bicyclo[2.2.2]octanones are presented. It is shown that for a number of carbons the chemical shifts cannot be predicted by a given additivity rule. The deviations of the observed chemical shifts from the calculated ones are discussed in terms of different interaction mechanisms operating through the σ bond frameworks or through space.     

Complete analysis of the 1H NMR spectra of acetylated glycals—a conformational study

The complete analysis of the ¹H NMR spectra of the six acetylated glycals as well as that of tetra-O-acetyl-2-hydroxy-D -glucal has been carried out. The conformation of these compounds, as determined from the proton couplings (±0.05Hz) obtained, has been interpreted in terms of a rapid interconversion equilibrium between the two possible dihydropyran half-chair conformations. A computer treatment of all observed couplings has been carried out to obtain optimized values for the populations and couplings characteristic of the two alternative half-chair conformations. The rotamer populations of the acetoxy–methyl group are discussed on the basis of the measured ⁵J₁₆ and ⁵J₃₆ couplings.     

Studies in organic mass spectrometry—XII: Mass spectra of chalcones and flavanones. The isomerisation of 2′-hydroxy-chalcone and flavanone

The mass spectra of isomeric 2′-hydroxy-chalcones and flavanones (i.e. 2-phenyl-chroman-4-ones) are essentially identical. Thermal isomerisation prior to ionisation was ruled out. A study of metastable transitions (first and second field free region of a double focusing instrument), as well as low energy spectra of both isomers, pointed towards completely identical fragmentation pathways for the two compounds. Five deuterated compounds were then investigated. The heats of formation of the most important ions were determined. It was concluded that an intramolecular equilibrium exists between a chalcone type and a flavanone type molecular ion.     

Chemistry of 6H-pyrido [4, 3-b] carbazoles. Part 10—Carbon-13 nuclear magnetic resonance spectra of ellipticines and some model compounds

The ¹³C NMR spectrum of ellipticine has been re-interpreted by reference to model compounds, and correlated with the spectra of a number of new ellipticine derivatives.     

Proton magnetic resonance spectra of some 6- and 7-substituted 2-amino-4-hydroxypteridines

The conformations in solution of 6-phenyltetrahydropterin, 6,7-diphenyltetrahydropterin and 6-7, dimethyltetrahydropterin have been determined from their proton magnetic resonance spectra. The 6-phenyltetrahydropterin has the reduced pyrazine ring in a half chair conformation with the phenyl ring in the equatorial position. Both the 6,7-diphenyl- and 6,7-dimethyltetrahydropterins are of the cis configuration and have one substituent in an axial position. The enzymatic activity of these cofactors may be related to these conformations.     

Studies in tertiary amine oxides part II—carbon-13 nuclear magnetic resonance spectra of selected acetylenic amines,their N-oxides and the Meisenheimer rearrangement products

Carbon-13 NMR chemical shifts and ¹J(CH), ²J(CH) and ³J(CH) coupling constants of selected saturated nitrogen heterocyclic molecules containing the acetylenic moiety have been determined. These NMR parameters have also been determined for the corresponding N-oxides and the Meisenheimer rearrangement products, the O-allenylhydroxylamines. The effect of the N-oxidation on the chemical shifts of the ring and the acetylenic carbon atoms is discussed.     

Quantitative analysis by nuclear magnetic resonance with fourier transformation: I—Proton case

For quantitative analysis by NMR spectroscopy with Fourier transform, the usual experimental conditions have to be partly modified. Careful regulation of the delays between the different phases of the process is particularly important. The filters of the spectrometer and the calculations on the free induction decay are important causes of error. Precise results are given.     

Nuclear magnetic resonance spectra of carbanions—III: Tetraphenylethylene dianion

The PMR spectra of the titled carbanion have been observed well-resolved and suitable for first-order analysis. Excess charges localized in the phenyl rings are estimated from the chemical shifts and compared with those observed in other carbanions.     

The NMR spectra of porphyrins. 27—proton NMR spectra of chlorophyll-a and pheophytin-a

The 500 MHz proton NMR spectra of chlorophyll-a in several non-aggregating solvents, at high dilution, are given and that of pheophytin-a in CDCl₃ at 360 MHz and at high dilution is reported. Under these conditions, the dispersion is such that separate resonances are observed and can be assigned for all protons in the molecules, except P-5 to P-15 in phytyl side-chain. The complex spin systems of the C-7 propionic ester side-chains, and of the P-1/P-2 fragment, are analysed and the couplings obtained are interpreted in terms of possible conformations of the side-chain.     

Carbon-13 nuclear magnetic resonance spectra. VIII—18α- and 18β-glycyrrhetic acid derivatives

The ¹³C NMR data of six pairs of 18α/18β-glycyrrhetic acid derivatives are presented. It is shown that the configuration at C-18 can easily be recognized by inspecting the chemical shifts of several characteristic carbons, e.g. C-12, C-13, C-18 and C-28. The shifts of these carbons originated by the change of the D/E ring junction proved to be largely independent of the substitution at C-3 and C-20.